Table of Contents

Chapter 1 (Introduction)

1.1 Background of the study--------------------------------------------------------------------3-5

1.2 Statement of the problem. ----------------------------------------------------5

1.3 Objectives of the study-------------------------------------------------------5-6

1.4 Scope of the study --------------------------------------------------------------------------6

1.5 Justification----------------------------------------------------------------------------------6

Chapter 2 (Literature Review)

2.1. Corrosion-----------------------------------------------------------------------------------7

2.2. Chemistry of Corrosion------------------------------------------------------------------7-10

2.3. Types of Corrosion. ----------------------------------------------------------------------11

2.3.1. General attack corrosion. --------------------------------------------------------------11-13

2.3.2. Localized corrosion. --------------------------------------------------------------------13-36

 Pitting Corrosion.
 Crevice Corrosion
 Thermogalvanic Corrosion
 Fretting Corrosion
 Microbial Corrosion
 Galvanic Corrosion
 Intergranular Corrosion
 Stray Current Corrosion
 Corrosion Fatigue
 Erosion Corrosion

1
 Stress Corrosion Cracking (SCC)
 Hydrogen Damage

2.4. The Consequences of Corrosion--------------------------------------------------------------37

2.5. Prevention Of Corrosion----------------------------------------------------------------------38

2.5.1. Cathodic Protection--------------------------------------------------------------------------39

2.5.2. Protective Coating and Linings------------------------------------------------------------39-40

2.5.3. Material Selection---------------------------------------------------------------------------41-42

2.5.4. Corrosion inhibitor--------------------------------------------------------------------------42-44

2.6. Corrosion Monitoring-------------------------------------------------------------------------44-45

2.6.1. Corrosion Techniques-----------------------------------------------------------------------45-50

2.6.2. Applications of Corrosion Monitoring Techniques------------------------------------51

2.7. Review of Related Works--------------------------------------------------------------------51-60

Chapter 3(Methodology)

3.1. Experimental Methodology------------------------------------------------------------------61

3.1.1. Materials and Equipment------------------------------------------------------------------61

3.1.2. Procedure------------------------------------------------------------------------------------62-63

3.1.3. Measurement of weight loss and corrosion rate determination------------------64

3.2. Mathematical Methodology----------------------------------------------------------------64-66

References-----------------------------------------------------------------------------------------67-96

2
 CHAPTER ONE

INTRODUCTION
1.1 Background of the study.

Corrosion is the degradation of materials properties due to interactions with the environments. It

is a natural phenomenon most commonly associated with metals. When these metals react

chemically with their environment, they tend to corrode, losing their physical and chemical

properties, and then retarding to a more stable form- its oxide or hydroxide. The most common

example of corrosion is rust; most profound in iron. Apart from metals, all material types all

undergo degradation, including polymeric materials (insulators on wiring), ceramics. (Shaw et al,

2006)

Corrosion can come in different forms. Many of these forms have been classified by the

international scientific literature (Raffaele, 2010).

The first classification is made on the basis of the reaction that takes place on the metal surface.

This reaction could either be a chemical or electrochemical corrosion. While chemical corrosion

involves reaction between chemicals, it occurs when two compounds or elements react

chemically. Electrochemical corrosion involves two half-cell reactions; an oxidation reaction at

the anode and a reduction at the cathode.

The second classification is based on the appearance and the basic forms of corrosion. These

basic forms could either be uniform or localized. Hence, we have the general corrosion; uniform

corrosion, galvanic corrosion, pitting corrosion, crevice corrosion, erosion corrosion, cavitation

corrosion, fatigue corrosion and stress corrosion.

3
There is also classification on the basis of corrosive environment. They include: gaseous

corrosion, microbial corrosion and bacteria corrosion, marine corrosion, underground corrosion

and atmospheric corrosion.

The world corrosion organization estimates the global cost of corrosion to be roughly 2.2 trillion

US dollars annually (Lambert Academic Publishing, 2014). Several studies over the past 30

years have shown that the cost of corrosion in the industrial sector annually is approximately

3.1% of the country‟s Gross National Product (GNP). (Shaw, 2006). The damage caused by

corrosion results to expensive maintenance and replacements which would be uneconomical for

the organization.

In addition, a lot of work has been done on the various forms of corrosion, some focusing on

developing models in determining the rate of corrosion of metals in different environments. But

many of the literatures on corrosion modeling have been centered on acidic medium, a particular

type of corrosion, the impact of climatic change on atmospheric corrosion, CO2 corrosion et al.

The object of this study is to do a statistical study of the rate of corrosion of mild steel in a salty

medium. This could be termed marine corrosion. The reason for this study is that some industries

(mining, thermoelectric power) make use of saline water in their operations. Seawater systems

used by many of the industries such as shipping, oil and gas etcetera are used for cooling

purposes, firefighting, oil field water injection and for desalination plants. The seawater systems

are also used for generating electricity through turbines, manufacturing of bio-insecticides,

methanol. In addition, seawater systems are also used for air-conditioning.

Although the sea water is used for all these purposes, it causes the corroding of the metallic parts

of these systems, thereby leading to their failures. More so, the shipping industry faces a great

challenge in combating corrosion attacks on their vessels. In US, the shipping industry estimates

4
about 2.7 billion dollars spent annually in combating corrosion (NACE International, leaders in

corrosion control technology). Hence, this work serves the purpose of bringing to limelight the

rate at which corrosion takes place in sea water environments.

1.2 Statement of the problem.

Many of the works done on corrosion modeling has been centered on acidic mediums, (Amani,

2010; Suleiman, 2013). Some are also centered on a particular form of corrosion that is probably

peculiar to an environment, (Velazquez, 2014).These works and many others that are not listed

here serves great purposes as these studies and models have been used to combat corrosion in the

past years.

But few of the published works have centered on marine corrosion which ought not to be

because, the cost of marine corrosion has been on the increase. As stated earlier, the cost of

combating corrosion attacks on vessels, systems and equipment placed on the sea is alarming.

Hence this work is important to help marine engineers and equipment designershave first-hand

information on marine corrosion so that when they are designing seawater systems or any

equipment (metallic) to be used in the saline environment, they would be able to improve on the

properties of the metallic framework so as to avoid adverse and early corrosion attacks.

1.3 Objectives of the study

The main objective of this article is to study the kinetics of the rate of corrosion of mild steel in a

saline environment.

The specific objectives are:

1. To study the corrosion behavior of mild steel in saline environment

5
2. To measure the rate of corrosion using the weight loss method

3. To model the corrosion rate kinetically as a factor of different concentrations of salt solutions

and time

4. To analyze the results and provide constructive recommendation.

1.4 Scope of the study

This work is aimed at determining the rate at which salt water corrodes mild steels. The factors

that are considered here are salt solution concentrations and time. Although, it is generally

known that increase in salt concentration increases the rate of corrosion, this work is aimed at

determining the connection between salinity and corrosion rate on the basis of dissolved oxygen

concentration.

1.5 Justification

The rate at which sea equipment, vessels and systems corrode has been alarming. As stated in the

background study, the amount of money lost to corrosion is enormous. If the order of reaction

and corrosion rate is determined:

 It can be used to properly design part of offshore equipment to ensure they have the required

thickness.

 It can be used to determine when certain parts of equipment should be replaced

 It can help determine choice of metal to be used at different salt concentrations in sea water

 It can be used to effectively choose and plan effective corrosion inhibition technique.

6
 CHAPTER TWO

LITERATURE REVIEW
2.1 Corrosion

From the journals published by the National Association of Corrosion Engineers (NACE),

corrosion is defined as the deterioration of a metal as a result of chemical reactions between it

and the surrounding environment (Terence, 2016). Like other natural hazards such as

earthquakes or severe weather disturbances, corrosion can cause dangerous and expensive

damage to a lot of things from vehicles, home appliances, water systems, pipelines, bridges and

public buildings. Unlike weather-related disasters, however, there are time-proven methods to

prevent and control corrosion that can reduce or eliminate its impact on public safety, the

economy and the environment. The type of metal and the environmental conditions, particularly

what gases that are in contact with the metal, determine the form and rate of deterioration.

2.2 Chemistry of Corrosion

Common structural metals are obtained from their ores or naturally-occurring compounds by the

expenditure of large amounts of energy. These metals can therefore be regarded as being in a

metastable state and will tend to lose their energy by reverting to compounds more or less similar

to their original states. Since most metallic compounds, and especially corrosion products, have

little mechanical strength, a severely corroded piece of metal is quite useless for its original

purpose.

Virtually all corrosion reactions are electrochemical in nature, at anodic sites on the surface the

metal goes into solution as ferrous ions, thus constituting the anodic reaction. As metals undergo

7
oxidation to ions they release electrons whose negative charge would quickly build up in the

metal and prevent further anodic reaction, or corrosion. Thus this dissolution will only continue

if the electrons released can pass to a site on the metal surface where a cathodic reaction is

possible. At a cathodic site the electrons react with some reducible component of the electrolyte

and are themselves removed from the metal. The rates of the anodic and cathodic reactions must

be equivalent according to Faraday‟s Laws, being determined by the total flow of electrons from

anodes to cathodes which is called the “corrosion current”.

Since the corrosion current must also flow through the electrolyte by ionic conduction the

conductivity of the electrolyte will influence the way in which corrosion cells operate. The

corroding piece of metal is described as a “mixed electrode” since simultaneous anodic and

cathodic reactions are proceeding on its surface. The mixed electrode is a complete

electrochemical cell on one metal surface.

The most common and important electrochemical reactions in the corrosion of iron are thus:

Fe--->Fe2++2e- Anodic reaction (2.1)

2H+ + 2e ---> H2 Cathodic reaction (2.2)

The anodic and cathodic reaction brings about the formation of solid corrosion debris products

[iron (II) hydroxide].

Fe2++2OH- ---> Fe(OH) 2[iron (II) hydroxide] (2.3)

Pure iron (II) hydroxide is white but the material initially produced by corrosion is normally a

greenish color due to partial oxidation in air.

8
 2Fe (OH) 2 + H2O +1/2O2----->2Fe (OH) 3 [iron (III) hydroxide] (2.4)

Further hydration and oxidation reactions can occur and the reddish rust (iron (III) hydroxide)

that eventually forms is a complex mixture whose exact constitution will depend on other trace

elements which are present. Because the rust is precipitated as a result of secondary reactions it

is porous and absorbent and tends to be harmful. This encourages further corrosion.

For other metals or different environments different types of anodic and cathodic reactions may

occur. If solid corrosion products are produced directly on the surface as the first result of anodic

oxidation these may provide a highly protective surface film which retards further corrosion, the

surface is then said to be “passive”. An example of such a process would be the production of an

oxide film on iron in water, a reaction which is encouraged by oxidizing conditions or elevated

temperatures.

2Fe + 3H2O → Fe2O3 + 6H+ + 6e (2.5)

There are certain factors that tend to increase the rate of corrosion. These factors include:

 Establishment of well-defined locations on the surface for the anodic and cathodic reactions.

This concentrates the damage on small areas where it may have more seriouseffects, this

being described as “local cell action”. Such effects can occur when metals of differing

electrochemical properties are placed in contact, giving a “galvanic couple”.

Galvanic effects may be predicted by means of a study of the Galvanic Series which is alist

of metals and alloys placed in order of their potentials in the corrosive environment,such as

9
 sea water. Metals having a more positive (noble) potential will tend to extractelectrons from

a metal which is in a more negative (base) position in the series and hence accelerate its

corrosion when in contact with it. The Galvanic Series should not be confused with the

Electrochemical Series, which lists the potentials only of pure metals in equilibrium with

standard solutions of their ions. Galvanic effects can occur on metallic surfaces which

contain more than one phase, so that “local cells” are set up on the heterogeneous surface.

Localized corrosion cells can also be set up on surfaces where the metal is in a varying

condition of stress, where rust, dirt or crevices cause differential access of air, where

temperature variations occur, or where fluid flow is not uniform.

 Stimulation of the anodic or cathodic reaction. Aggressive ions such as chloride tend

toprevent the formation of protective oxide films on the metal surface and thus

increasecorrosion. Sodium chloride is encountered in marine conditions and is spread on

roadsin winter for de-icing.

 Quite small concentrations of sulphur dioxide released into the atmosphere by thecombustion

of fuels can dissolve in the invisibly thin surface film of moisture which isusually present on

metallic surfaces when the relative humidity is over 60-70%. Theacidic electrolyte that is

formed under these conditions seems to be capable ofstimulating both the anodic and the

cathodic reactions ( Ashevoth et al, n.d)

10
2.3 Types of Corrosion.

The most common type of corrosion is rust. The reddish-brown compound referred to as rust is

iron oxide (Fe2O3). It is as a result of the reactions between oxygen and iron. There are different

types of corrosion; each can be classified by the cause of the metal‟s chemical deterioration.

2.3.1 General attack corrosion.

This is also known as uniform attack corrosion; general attack corrosion is the most common

type of corrosion and is caused by a chemical or electrochemical reaction that results in the

deterioration of the entire exposed surface of a metal. It accounts for the greatest amount of

metal destruction by corrosion, but is considered as a safe form of corrosion, due to the fact that

it is predictable, manageable and often preventable (Bell, 2016).

General attack corrosion proceeds more or less uniformly over an exposed surface without

appreciable localization. This leads to relatively uniform thinning on one side or the other (or

both) for pipe and tubing. It is recognized by a roughening of the surface and usually by the

presence of corrosion products. The mechanism of the attack typically is an electrochemical

process that takes place at the surface of the material. Differences in the composition or

orientation between small areas on the metal surface create anodes and cathodes that facilitate

the corrosion process (National Association of Corrosion Engineers, 2000).

Most often caused by misapplying materials in corrosive environments, general corrosion often

can be tolerated because the effect of metal loss is relatively easy to assess and allowances can

be made in the initial design. General corrosion is a type of corrosion that takes place at almost

the same rate on the surface of the entire metal that is exposed to the corrosion-causing

11
 conditions. The surface that results from the corrosion process can have areas where there is

either more or less penetration. In such cases, several minimum penetrations can lead to a

maximum penetration. As a result of these, the corroded surfaces have a mottled appearance. It is

also referred to as uniform corrosion.

In addition, this type of corrosion is normally featured by an attack that appears to be uniform in

nature. This uniformity is usually spread on the entire surface of the metal, leading to a smooth

appearance. The attack that leads to corrosion on the surface of the metal is the result of the

material being subjected or exposed to a medium that is corrosive in nature. Because of this, the

corrosion rate is hence defined as the loss of mass per unit of surface area. In other words, the

corrosion rate of a metal can be expressed as mean loss of metal per unit over time, or units of

mm per year.

General corrosion is most likely to be caused by alkaline solutions or strong acidic mediums. The

factors leading to corrosion can either be increased or decreased depending on the addition of

reducing or oxidizing components. With different additives, there can be a great variance in the

performance of the metal, depending on the additives used.

Uniform corrosion can be slowed down or stopped by using three (3) basic facts:

I. Slow down or stop the movement of electrons.

This can be achieved by coating the surface with a non-conducting medium such as paint,

lacquer or oil. Also by reducing the conductivity of the solution in contact with the metal; an

extreme case being to keep it dry. The conductive pollutants could be washed away regularly.

In addition, current can be applied to the material.

II. Slow down or stop oxygen from reaching the surface. Coating the metal can achieve this.

12
III. Another way of stopping this form of corrosion is by preventing the metal from giving up

electrons by using a more resistant metal higher in the electrochemical series. Metals that

forms an oxide that is protective and stops the reaction. An example of this is aluminum.

(Nimmo et al, 2003)

2.3.2 Localized corrosion.

As against uniform corrosion, localized corrosion only affects a targeted area on the metal.

Localized corrosion can be:

 Pitting

 Crevice

 Galvanic corrosion

 Pitting corrosion

 Stray current corrosion

 Microbial corrosion

 Intergranular corrosion

 Crevice corrosion

 Thermogalvanic corrosion

 Corrosion caused by combined action

 Corrosion fatigue

 Fretting corrosion

 Stress corrosion cracking

 Hydrogen damage

 Erosion Corrosion

13
Pitting Corrosion.

Pitting results when a small hole or cavity forms in the metal, usually as a result of de-

passivation of a small area.The pitted area becomes cathodic, producing a localized galvanic

reaction. The deterioration of this small area penetrates the metal and can lead to failure. This

form of corrosion is often difficult to detect due to the fact that it is usually relatively small

and may be covered and hidden by corrosion-produced compounds. (Bell, 2016).

The driving power for pitting corrosion is the

depassivation of a small area, which becomes

anodic while an unknown but potentially vast area

becomes cathodic; leading to very localized

galvanic corrosion. The corrosion penetrates the

mass of the metal, with limited diffusion of ions.

The mechanism of pitting corrosion is probably the

same as crevice corrosion. The more accepted

explanation for pitting corrosion is that is an Figure 1: Pitting Corrosion

autocatalytic process. Metal oxidation results in localized acidity that is maintained by the

spatial separation of the cathodic and anodic half-reactions, which creates a potential gradient

and electro migration of aggressive anions into the pit (ASM International, 1987).

Pitting corrosion is extremely insidious, as it causes little loss of material with small effect on

its surface, while it damages the deep structures of the metal. The pits on the surface are

often obscured by corrosion products. Pitting can be initiated by a small surface defect, being

14
a scratch or a local change in composition, or damage to protective coating. Polished surfaces

display higher resistance to pitting.

Pitting corrosion only occurs for specific alloy/environment combinations. Hence, pitting

corrosion occurs in alloys that are protected by a tenacious (passivating) oxide film such as

stainless steels, nickel alloys, aluminum alloys in environments that contain an aggressive

species such as chlorides (Cl-). In contrast, alloy/environment combinations where the

passive film is not very protective usually will not produce pitting corrosion. An example of

the importance of environment/alloy combinations is carbon steel. In environments where the

pH is less than 10, carbon steel does not form a passivating oxide film and the addition of

chloride results in uniform attack over the entire surface. However, at pH greater than 10, the

oxide is very protecting and the addition of chloride results in pitting corrosion.(ASM

International, 1987).

Apart from chlorides, other anions implicated in pitting include thiosulfates (S2O32-),

fluorides and iodides. Stagnant water conditions favor pitting. Thiosulfates are particularly

aggressive species and are formed by partial oxidation of pyrite, or partial reduction of

sulfate. Thiosulfates are a concern for corrosion in many industries.

A single pit in a critical point can cause a great deal of damage. An example is the explosion

in Guadalajara, Mexico on April 22, 1992, when gasoline fumes accumulated in sewers

destroyed kilometers of streets. The vapors originated from a leak of gasoline through a

single hole formed by corrosion between a steel gasoline pipe and a zinc-plated water pipe.

15
Fire arms can also suffer from pitting, most notably in the bore of the barrel when corrosive

ammunition is used and the barrel is not cleaned soon afterward. The deformities caused by

pitting can greatly reduce the firearm‟s accuracy. To prevent pitting in firearms bores, most

modern firearms have a bore lined with chromium

Pitting corrosion is one out of the numerous threats that affect pressure vessels and causes

failure of buried pipelines that convey materials like crude oil, gas and hydrocarbon. This

form of corrosion is more dangerous than uniform corrosion damage because it is more

difficult to detect, predict and design against. Corrosion products usually cover the pits. A

small, narrow pit with minimal overall metal loss can lead to the failure of an entire

engineering system. Pitting corrosion, which, for example, is almost a common denominator

of all types of localized corrosion attack, may assume different shapes.

Pitting corrosion can produce pits with their mouth open (uncovered) or covered with a semi-

permeable membrane of corrosion products. Pits can be either hemispherical or cup-shaped

(Velazquez et al, 2014)

Pitting is caused by:

 Localized chemical or mechanical damage to the protective oxide film, low dissolved

oxygen concentrations (which tend to render a protective oxide film less stable) and high

concentrations of chloride (as in seawater)

 Localized damage to, or poor application of, a protective coating.

 The presence of non-uniformities in the metal structure of the component, e.g.

nonmetallic inclusions.

16
A local cell that leads to the initiation of a pit can be caused by an abnormal anodic site

surrounded by normal surface which acts as a cathode, or by the presence of an abnormal

cathodic site surrounded by a normal surface in which a pit will have disappeared due to

corrosion.In the second case, post examination should reveal the local cathode, since it will

remain impervious to the corrosion attack. Most cases of pitting are believed to be caused by

local cathodic sites in an otherwise normal surface. Apart from causing loss of thickness,

corrosion pits can also cause stress in the metal.

Below are some definitions related to pitting corrosion:

Pitting factor: ratio of the depth of the deepest pit resulting from corrosion divided by the

average penetration as calculated from weight loss.

Pitting resistance equivalent number (PREN): This is an empirical relationship to predict the

pitting resistance of austenitic and duplex stainless steels. It is expressed as

PREN = Cr + 3.3 (Mo + 0.5W) +16N (2.6)

Through pits (narrow, deep, shallow, wide, elliptical, vertical grain attack) and sideway pits

(subsurface, undercutting, horizontal grain attack) are types of pitting corrosion. (National

Association of Corrosion Engineers, 2000).

17
Crevice Corrosion

This is similar to pitting corrosion in the sense that it occurs at a specific location. This type

of corrosion is often associated with a stagnant micro-environment, like those found under

gaskets and washers and clamps. Acidic conditions or a depletion of oxygen in a crevice can

lead to crevice corrosion. (Bell, 2016).

If two areas of a component in close proximity differ in the amount of reactive constituent

available, the reaction in one of the areas is speeded up. An example of this is crevice

corrosion which occurs when oxygen cannot penetrate a crevice and a differential aeration

cell is set up. (Nimmo et al, 2003)

Crevices make a chemical environment which is different from that of freely exposed

surfaces and therefore accelerate corrosion. This environment keeps moisture, traps

pollutants, concentrates corrosion products and meanwhile excludes oxygen. Most cases of

crevice corrosion occur in near-neutral solutions in which dissolved oxygen is the cathode

reactant. The crevices in which crevice corrosion happens may be formed by:

1. The geometry of the structure, e.g. riveted plates welded fabrications, threaded joints.

2. Contact of the metal with non-metallic solids, e.g. plastics, rubber, glass.

3. Deposits of sand, dirt or permeable corrosion products on the metal surface (a type of

crevice corrosion that is referred to as deposit attack).

Corrosion requires energy. During corrosion the reacting components go from a higher to a

lower energy state and release the energy needed for the reaction. In dry corrosion the metal

and the oxygen combine to produce the oxide on the surface because the reaction leads to a

18
compound (the oxide) at a lower energy level. The oxide layer shields the metal from the

oxygen and forms a barrier. The oxide will not react with the oxygen in the air or the metal.

The barrier makes it difficult for oxygen in the air to contact the metal and it eventually

grows so thick that the movement of electrons and ions across it stop. Provided the oxide

layer does not crack, or is not removed, the metal is protected from further corrosion.

The Fontana and Greene model describes crevice corrosion mechanism. This model consists
of four stages.

Stage 1: Corrosion occurs as normal both inside and outside the crevice:

Anodic reaction: M---->Mn++ne (2.7)

Cathodic reaction: O2 + 2H2O + 4e----> 4OH- (2.8)

The positively charged metallic ions are electrostatically counterbalanced by OH-.

Stage 2: At this stage, the cathodic reaction inside the crevice consumes most of the oxygen

available.

Stage 3: Cl- and OH- diffuse intothe crevice to maintain a minimum potential energy. Metal

chloride is formed. Hydrolysis of metal chloride lowers pH and

MCln + nH2O = M(OH)n + nHCl. (2.9)

Stage 4: More Mn+ ions attack more Cl- leads to lower pH inside crevice, metal dissolution

accelerates and more Mn+ ions will be produced that will lower pH. (Rashidi, 2007)

19
Corrosion occurs rapidly in the area with less oxygen. The potential for crevice corrosion can

be reduced by:

 Avoiding sharp corners and designing out stagnant areas

 Use of sealants

 Use welds instead of bolts or rivets

 Selection of resistant materials.

Thermogalvanic Corrosion

Thermogalvanic corrosion is a type of corrosion that results from the action of temperature

differences in electrolysis. The two metal electrodes in an electrolyte have different

potentials; hence the anode corrodes more than the cathode.

Thermogalvanic corrosion is encountered mostly in heat exchangers where there are

temperature differences. The region with the higher temperature in the metal acts as the

anode, and the cooler acts as the cathode. The anode undergoes high rates of Thermogalvanic

corrosion, which is associated with high temperatures. When the temperature of a material

changes, the rate of corrosion also changes in accordance to the rule that states: for every 10

degree rise in temperature, the rate of reaction doubles. The resulting attack of metal occurs

in between the minimum and maximum temperatures. In summary, Thermogalvanic

corrosion is a form of galvanic action in which metal dissolves from one surface and deposits

on another as the result of a temperature difference between the two surfaces.

20
Thermogalvanic corrosion can be prevented by using any of the following methods:

 Designing the component to reduce the thermal gradient

 Supplying a coolant in the component to minimize temperature differences

 Galvanic corrosion-resistant coatings made of steel alloys and iron. These are coatings

that slowly corrode while simultaneously minimizing steel corrosion. This method of

Thermogalvanic corrosion prevention has been used in bridges in coastal regions and

wind energy windmills.(Nimmo et al, 2003)

Fretting Corrosion

Fretting corrosion is caused by relative

motion between two surfaces in contact

by a stick-slip action causing breakdown

of protective films or welding of the

contact areas, allowing other corrosion

mechanisms to operate. (Nimmo et al,

2003).

Figure 2: Fretting Corrosion

This form of corrosion is induced under load and in the presence of repeated relative surface

motion or vibration. Pits characterize the damage caused by fretting corrosion. Also, contact

surfaces that experience vibrations are subjected to this form of corrosion. The most common

type of fretting is caused by vibration.

21
Fretting can also be definedas the wearing and sometimes corrosion damage at the asperities

of contact surfaces. This damage is induced under load and in the presence of repeated

relative surface motion, as induced for example by vibration. The ASM Handbook on

Fatigue and Fracture defines fretting as: "A special wear process that occurs at the contact

area between two materials under load and subject to minute relative motion by vibration or

some other force." Fretting tangibly downgrades the surface layer quality producing

increased surface roughness and micropits; which reduces the fatigue strength of the

components.

The contact movement causes mechanical wear and material transfer at the surface, often

followed by oxidation of both the metallic debris and the freshly exposed metallic surfaces.

Because the oxidized debris is usually much harder than the surfaces from which it came, it

often acts as an abrasive agent that increases the rate of both fretting and a mechanical wear

called false brinelling.

Fretting damage in steel can be identified by the presence of a pitted surface and fine 'red'

iron oxide dust resembling cocoa powder. Strictly this debris is not 'rust' as its production

requires no water. The particles are much harder than the steel surfaces in contact, so

abrasive wear is inevitable; however, particulates are not required to initiate fret.

Fretting decreases fatigue strength of materials operating under cycling stress. This can result

in fretting fatigue, whereby fatigue cracks can initiate in the fretting zone. Afterwards, the

crack propagates into the material. Lap joints, common on airframe surfaces, are a prime

location for fretting corrosion. This is also known as frettage or fretting corrosion.

22
The fundamental way to prevent fretting is to design for no relative motion of the surfaces at

the contact. Surface roughness plays an important role as fretting normally occurs by the

contact of the asperities of the mating surfaces. Lubricants are often employed to mitigate

fretting because they reduce friction and inhibit oxidation.

Soft materials often exhibit higher susceptibility to fretting than hard materials of a similar

type. The hardness ratio of the two sliding materials also has an effect on fretting wear.

However, softer materials such as polymers can show the opposite effect when they capture

hard debris which becomes embedded in their bearing surfaces. They then act as a very

effective abrasive agent, wearing down the harder metal with which they are in contact.

(Lipson et al, 1961).

Microbial Corrosion

Microbial corrosion is a form of bio deterioration and isfrequently referred to as biocorrosion

or microbial influenced corrosion (MIC). This degradation processprimarily acts on metals,

metalloids, minerals, and otherrock-based materials. Aside from bacteria, fungi, microalgae,

and naturally occurring organic/inorganicchemicals contribute to biocorrosion.

Many different bacterial genera are associated with MICand are often categorized by their

respiration techniques.Some common examples of these are:

Sulfate-reducing bacteria (SRB). They include: Desulfuromonas sp.,Desulfobacter sp., and

Desulfococcussp., etc. The SRB are strictly anaerobic.

23
Sulfur-oxidizing bacteria (SOB): They are primarily of the genusThiobacillus. These

organisms notably form sulfuric acidduring oxidation, and are capable of both oxidizing

sulfurand ferrous iron.

Ironbacteria (IO): They are of two types. The stalked (notably Gallionella sp.)

andfilamentous(Leptothrix sp., Clonothrix sp., Sphaerotilussp).These bacteria primarily

oxidize or reduce ironspecies during respiration.

There are many other miscellaneous groups of bacteria thatuse or respire metallic substances

and contribute tobiocorrosion. Some Pseudomonas species can reduce iron,while other

bacterial species can oxidize/reduce lessabundant metals like manganese, palladium, nickel,

etc.There are also biocorrosive bacteria that do not utilizemetals but secrete organic acids

which can break downsurrounding materials. It is important to note that not allspecies within

a genus induce MIC and not all perform thesame types of respiration.(Beech et al, 2004).

There are about a dozen of bacteria known to causemicrobiologically influenced corrosion of

carbon steels, stainless steels, aluminum alloys and copper alloys inwaters and soils with pH

4-9 and temperature 10-50oC.These bacteria can be broadly classified as aerobic(requires

oxygen to become active) or anaerobic (oxygen istoxic to the bacteria). Sulphate reducing

bacteria (SRB) isanaerobic and is responsible for most instances ofaccelerated corrosion

damages to ships and offshore steelstructures. Iron and manganese oxidizing bacteria are

aerobic and are frequently associated with acceleratedpitting attacks on stainless steels at

welds.

Many industries are affected by microbial corrosion. Some of these industries include:

24
 Chemical processing industries: stainless steel tanks, pipelines and flanged joints, particularly

in welded areasafter hydro testing with river or well waters.

 Nuclear power generation: carbon and stainless steelpiping and tanks; copper-nickel,

stainless, brass andaluminum bronze cooling water pipes and tubes,especially during

construction, hydrotest, and outageperiods.

 Onshore and offshore oil and gas industries: mothballedand water flood systems; oil and gas

handling systems,particularly in those environments soured by sulfate reducing bacteria

(SRB)-produced sulfides

 Underground pipeline industry: water-saturated clay-type soils of near-neutral pH with

decaying organic matterand a source of SRB.

 Water treatment industry: heat exchangers and piping

 Sewage handling and treatment industry: concrete and reinforced concrete structures

 Highway maintenance industry: culvert piping

 Aviation industry: aluminum integral wing tanks and fuelstorage tanks.(Garvenick, 1994)

Galvanic Corrosion

Galvanic corrosion also called dissimilar metal corrosionrefers to the corrosion damageinduced

when two dissimilar materials are coupled in acorrosive electrolyte. It is an electrochemical

process in whichone metal corrodes preferentially to another when bothmetals are in electrical

contact; in the presence of anelectrolyte. It occurs when two (or more)dissimilar metals are

brought into electrical contact underwater. When a galvanic couple forms, one of the metals

inthe couple becomes the anode and corrodes faster than itwould all by itself, while the other

25
becomes the cathode andcorrodes slower than it would alone.Either (or both) metal in the couple

may or may not corrodeby itself (themselves).

From the journals published by the National Association of Corrosion Engineers (NACE), the

driving force for this form of corrosion is a potential differencebetween the different materials.

Thesacrificial corrosion of one metal such as zinc, magnesiumor aluminum is a widespread

method of cathodicallyprotecting metallic structures.In a bimetallic couple, the less noble

material will becomethe anode of this corrosion cell and tend to corrode at anaccelerated rate,

compared with the uncoupled condition.The more noble material will act as the cathode in

thecorrosion cell. Galvanic corrosion can be one of the mostcommon forms of corrosion as well

as one of the mostdestructive.

Dissimilar metals and alloys have different electrodepotentials, and when two or more come into

contact in anelectrolyte, one metal acts as anode and the other ascathode. The electro potential

difference between thedissimilar metals is the driving force for an acceleratedattack on the anode

member of the galvanic couple. Theanode metal dissolves into the electrolyte, and

depositcollects on the cathodic metal.

The electrolyte provides a means for ion migration wherebymetallic ions move from the anode to

the cathode within themetal. This leads to the metal at the anode corroding morequickly than it

otherwise would and corrosion at the cathodebeing inhibited. The presence of an electrolyte and

anelectrical conducting path between the metals is essentialfor galvanic corrosion to occur.

In some cases, this type of reaction is intentionallyencouraged. For example, low-cost household

batteriestypically contain carbon-zinc cells. As part of a closedcircuit (the electron pathway), the

zinc within the cell willcorrode preferentially (the ion pathway) as an essential partof the battery

26
producing electricity. Another example is thecathodic protection of buried or submerged

structures. Inthis case, sacrificial anodes work as part of a galvaniccouple, promoting corrosion

of the anode, while protectingthe cathode metal.

The relative nobility of a material can be predicted bymeasuring its corrosion potential. The

well-known galvanicseries lists the relative nobility of certain materials in seawater. A small

anode/cathode area ratio is highlyundesirable. In this case, the galvanic current isconcentrated

onto a small anodic area. Rapid thickness lossof the dissolving anode tends to occur under

theseconditions. Galvanic corrosion problems should be solvedby designing to avoid these

problems in the first place.

Galvanic corrosion cells can be set up on the macroscopiclevel or on the microscopic level. On

the microstructurallevel, different phases or other microstructural features canbe subject to

galvanic currents. (Wheelar et al, 1972).

In summary, for galvanic corrosionto occur, three conditions must be present:

1. Electrochemically dissimilar metals must be present

2. These metals must be in electrical contact, and

3. The metals must be exposed to an electrolyte

A common example of galvanic corrosion is the rusting ofcorrugated iron sheet, which becomes

widespread when theprotective zinc coating is broken and the underlying steel isattacked. The

zinc is attacked preferentially because it isless noble, but once it has been consumed, rusting of

thebase metal can occur in earnest. By contrast, with atraditional tin can, the opposite of a

27
protective effect occurs:because the tin is nobler than the underlying steel,when the tin coating is

broken, the steel beneath isimmediately attacked preferentially.

Intergranular Corrosion

Intergranular corrosion is localized attack along the grain boundaries, or immediately adjacent to

grain boundaries, while the bulk of the grains remain largely unaffected. This form of corrosion

is usually associated with chemical segregation effects (impurities have a tendency to be

enriched at grain boundaries) or specific phases precipitated on the grain boundaries. Such

precipitation can produce zones of reduced corrosion resistance in the immediate vicinity.

The attack usually progresses along a narrow path along the grain boundary and, in a severe case

of grain-boundary corrosion; entire grains may be dislodged due to complete deterioration of

their boundaries. In any case the mechanical properties of the structure will be seriously affected.

A classic example is the sensitization of stainless steels or weld decay. Chromium-rich grain

boundary precipitates lead to a local depletion of Cr immediately adjacent to these precipitates,

leaving these areas vulnerable to corrosive attack in certain electrolytes. Reheating a welded

component during multi-pass welding isa common cause of this problem.

From the journals published by the National Association of Corrosion Engineers (NACE),

Exfoliation corrosion is a further form of Intergranular corrosion associated with high strength

aluminum alloys. Alloys that have been extruded or otherwise worked heavily, with a

microstructure of elongated, flattened grains, are particularly prone to this damage. Corrosion

products building up along these grain boundaries exert pressure between the grains and the end

result is a lifting or leafing effect. The damage often initiates at end grains encountered in

machined edges, holes or grooves and can subsequently progress through an entire section.

28
Intergranular corrosion (IGC) is a selective attack in the vicinity of the grain boundaries of a

stainless steel. It is as a result of chromium depletion, mainly due to the precipitation of

chromium carbides in the grain boundaries. Chromium carbides can be precipitated if the

stainless steel is sensitized in the temperature range 550–850oC (1020–1560oF), for example

during heat treatment or welding. If the temperature lies in the critical range for too long,

chromium carbides will start to form in the grain boundaries, which then become susceptible to

Intergranular corrosion. The area adjacent to the grain boundaries becomes depleted in

chromium (the chromium reacts with carbon and forms carbides) and this zone, therefore,

becomes less resistant to Intergranular corrosion.(ASTM A262 Intergranular corrosion Testing

of stainless steels).

To reduce the risk of Intergranular corrosion, materials with less than 0.05% carbon normally

have sufficient resistance against Intergranular corrosion after welding. ELC (extra low carbon

content) steels, i.e. steels with maximum 0.030% carbon, have very good resistance to

Intergranular corrosion. The same applies to steels stabilized with titanium (Ti) or niobium (Nb),

since thesetypes of steel form niobium or titanium carbides instead ofchromium carbides, thus

avoiding the critical decrease inthe chromium content.

Stray Current Corrosion

Stray current corrosion orstray current electrolysis refers to corrosion resulting fromstray current

-current flowing through paths other than the intended circuit.The process of stray current

corrosion is electrolytic innature. The extent of damage or loss of metal is directly proportional

to the magnitude of stray current passingthrough the system. Underground pipelines and

29
storagetanks without cathode protection (CP) systems are particularly susceptible tostray current

corrosion. Stray current corrosion tends to belocalized, causing a concentration of pits that is

notnormally observed at locations where the stray current leaves metal structure.

Figure 3: Stray Current Corrosion

The stray currents responsible for this corrosion come fromDC distribution lines, railway

systems, substations, andalternating current, among other sources. These currentsthen flow

through steel structures or piping systems,causing corrosion.Stray current corrosion can be

compared to the galvaniccorrosion, where the current is internally generated,although different

remedial measures may be taken. Alsosimilar are the chemical and electrical reactions at

theelectrolyte and the metal interfaces. The anode is taken tobe the metal that corrodes, where

current flows to thecathode.

The most common factors that favor stray currentcorrosion include:

 High electrical resistance found on running rails.

 Poor installation of the running rails from the earth.

 The widely spaced substations that cause voltagedrops on the rails.

The corrosion may be rapid where the current produced bythe galvanic cells are less than the

stray current. Whencurrent leaves the metal to flow to the electrolyte medium,the part where the

30
current leaves undergoes severecorrosion. Some metals like aluminum can be destroyedvery

fast.For instance, a boat can act as a good ground for DCcurrents because of its low resistance

compared to thecurrent flowing all the way from the leaking boat throughthe water medium to

the ground. Corrosion will be severe atthe point where the current leaves the boat and travels

tothe ground.(Ghali, 2010).

The stray currents may be either external or internal, withthe internal ones causing electric shorts

in the wiring systemof the boat. The external sources are mainly the shorepower connections,

where a leaking boat will corrode otherboats on the same shore. This only happens when the

otherboats have better grounds compared to the one on the faultyboat.

Stray current corrosion is prevented through the use of agalvanic insulator. Modern measures

include decreasing theelectrical resistance, especially for the rail return circuit, andincreasing of

the electrical resistance between the groundand the rails. One safety regulation that can be

applied isthat a three-wire cable which should be used to carry theshore power from the boat.

One lead grounds all the otherelectrical equipment, thus reducing shock from the boats

This form of corrosion can also be prevented by identifying the source of stray current and then

stopping the leakage from the intended circuit by maintaininggood electrical connections and

insulation. Cathodic protection systems can also be installed to offset the effect of stray current.

Corrosion Fatigue

Corrosion Fatigue refers to theprocess in which a metal fractures prematurely underconditions of

simultaneous corrosion and repeated cyclicloading at lower stress levels or fewer cycles than

would berequired to cause fatigue of that metal in the absence of the corrosive

31
environment.Corrosion-fatigue is the result of the combined action of analternating or cycling

stresses and a corrosive environment.The fatigue process is thought to cause rupture of

theprotective passive film, upon which corrosion isaccelerated. If the metal is simultaneously

exposed to acorrosive environment, the failure can take place at evenlower loads and after

shorter time.In a corrosive environment the stress level at which it couldbe assumed a material

has infinite life is lowered orremoved completely. Contrary to a pure mechanical fatigue,there is

no fatigue limit load in corrosion-assisted fatigue.Corrosion fatigue and fretting are both in this

class. Muchlower failure stresses and much shorter failure times canoccur in a corrosive

environment compared to the situationwhere the alternating stress is in a non-

corrosiveenvironment.The fatigue fracture is brittle and the cracks are most oftentransgranular,

as in stress-corrosion cracking, but notbranched.(Karen, 2013).

Corrosion fatigue is fatigue in a corrosive environment. It isthe mechanical degradation of a

material under the jointaction of corrosion and cyclic loading. Nearly all engineeringstructures

experience some form of alternating stress, andare exposed to harmful environments during their

servicelife. The environment plays a significant role in the fatigueof high-strength structural

materials like steel, aluminumalloys and titanium alloys. Materials with high specificstrength are

being developed to meet the requirements ofadvancing technology. However,their usefulness

depends toa large extent on the extent to which they resist corrosionfatigue

Corrosion Fatigue can beprevented through reducing the fatigue by minimizing vibration and

pressurefluctuation. Also, this form of corrosion is reduced by using high-performance

alloysresistant to corrosion fatigue. In addition coatings and inhibitors could be put into place

todelay the initiation of corrosion fatigue cracks. (Kitegava, 1972).

32
Erosion Corrosion

Erosion corrosion is a degradation of material

surface dueto mechanical action, often by

impinging liquid, abrasion by slurry, particles

suspended in fast flowing liquid or

gas,bubbles or droplets, cavitation, etc.

Figure 4: Erosion Corrosion
(Dhawan et al, 2015).

From the journals published by the National Association of Corrosion Engineers (NACE), it is

acceleration in the rate of corrosionattack in metal due to the relative motion of a corrosive

fluidand a metal surface. The increased turbulence caused bypitting on the internal surfaces of a

tube can result in rapidlyincreasing erosion rates and eventually a leak. Erosioncorrosion can also

be aggravated by faulty workmanship.For example, burrs left at cut tube ends can upset

smoothwater flow, causing localized turbulence and high flowvelocities, resulting in erosion

corrosion. A combination oferosion and corrosion can lead to extremely high pittingrates.In

offshore well systems, the process industry inwhich components come into contact with sand-

bearingliquids, this is an important problem.High hardness in a material does not necessarily

guaranteea high degree of resistance to erosion corrosion.

Materials selection plays an important role in minimizingerosion corrosion damage. Caution is in

order whenpredicting erosion corrosion behavior on the basis ofhardness. High hardness in a

material does not necessarilyguarantee a high degree of resistance to erosion corrosion.

33
Design features are also particularly important.It is generally desirable to reduce the fluid

velocity andpromote laminar flow; increased pipe diameters are usefulin this context. Rough

surfaces are generally undesirable.Designs creating turbulence, flow restrictions andobstructions

are undesirable. Abrupt changes in flowdirection should be avoided. Tank inlet pipes should

bedirected away from the tank walls, towards the center.

Welded and flanged pipe sections should always becarefully aligned. Impingement plates of

baffles designed tobear the brunt of the damage should be easily replaceable.The thickness of

vulnerable areas should be increased.Replaceable ferrules, with a tapered end, can be

insertedinto the inlet side of heat exchanger tubes, to preventdamage to the actual tubes. Several

environmentalmodifications can be implemented to minimize the risk oferosion corrosion.

Abrasive particles in fluids can beremoved by filtration or settling, while water traps can beused

in steam and compressed air systems to decrease therisk of impingement by droplets. De-aeration

and corrosioninhibitors are additional measures that can be taken.Cathodic protection and the

application of protective coatingmay also reduce the rate of attack.

Stress Corrosion Cracking (SCC)

Stress corrosion cracking is cracking due to a process involving conjoint corrosion and straining

of a metal due to residual or applied stress. This form of corrosion involves the interaction

between corrosion and mechanical stress to produce failure by cracking. SCC is an insidious

form of corrosion that produces a marked loss of mechanical strength with little metal loss. The

damage is not obvious to casual inspection and the stress corrosion cracks can trigger mechanical

fast fracture and serious failure of components.(Afolabi et al, 2013)

34
 Figure 5: Stress Corrosion Cracking

For stress corrosion to occur, three requirements are to be met. They include:

 A susceptible material

 An environment that causes SCC for the material

 Sufficient tensile stress to induce SCC

The environment that can cause SCC could be chloride-bearing or hydrogen Sulphide media.

Chloride-induced SCC normally occurs over 60oC. The impact of SCC on a material usually

falls between dry cracking and the fatigue threshold of that material. Cold deformation and

forming, welding, heat treatment, machining and grinding can introduce residual stresses.

SCC usually occurs in certain specific alloy-environment-stress combinations. Macroscopically,

SCC fractures have a brittle appearance. This form of corrosion is very difficult to detect. The

best way of preventing this form of corrosion are: by adequately choosing the right materials,

reducing stress, removing critical environmental species such as hydroxides, chlorides and

oxygen and avoiding stagnant areas and crevices in heat exchangers where chloride and

hydroxide might become concentrated.

35
Hydrogen Damage

Hydrogen can cause a number of corrosion problems. Hydrogen embrittlement is a problem with

high-strength steels, titanium, and some other metals. One way of avoiding this is by using

resistant alloys. Hydrogen damage occurs when hydrogen enters steel as a result of the reduction

reaction on a metal cathode. Single-atom nacent hydrogen atoms then diffuse through the metal

until they meet with another atom, usually at inclusions or defects in the metal. The resultant

diatomic hydrogen molecules are then too big to migrate and become trapped. Finally, a gas

blister builds up and ma split the metal.

From the journals published by the National Association of Corrosion Engineers (NACE),

hydrogen damage involves the ingress of hydrogen into a metal, making the metal to lose its

ductility and load-bearing capacity. These eventually causes cracking and catastrophic brittle

failures at stresses below the yield stress of susceptible materials. Examples of hydrogen damage

include cracking of hardened steels when exposed to conditions which inject hydrogen into it.

Hydrogen damage comes in forms. These forms include: solid solution hardening, internal defect

creation, hydride embrittlement and hydrogen embrittlement.

Hydrogen damage is controlled by minimizing corrosion in acidic environments. It is not a

problem in neutral or caustic environment or with high-quality steels that have low impurity and

inclusions levels.

It should be noted that hydrogen damage is not a permanent condition. If cracking does not occur

and the environmental conditions are changed so that no hydrogen is generated on the surface of

the metal, the hydrogen can rediffuse from the steel, so that ductility is restored. (Avery et al,

2001)

36
2.4 The Consequences of Corrosion

The consequences of corrosion are many and varied and the effects of these on the safe, reliable

and efficient operation of equipment or structures are often more serious than the simple loss of a

mass of metal. Failures of various kinds and the need for expensive replacements may occur

even though the amount of metal destroyed is quite small. Some of the major harmful effects of

corrosion can be summarized as follows:

1. Reduction of metal thickness leading to loss of mechanical strength and structural failure or

breakdown. When the metal is lost in localized zones so as to give a crack like structure, very

considerable weakening may result from quite a small amount of metal loss.

2. Hazards or injuries to people arising from structural failure or breakdown (e.g. bridges, cars,

aircraft).

3. Loss of time in availability of profile-making industrial equipment.

4. Reduced value of goods due to deterioration of appearance.

5. Contamination of fluids in vessels and pipes (e.g. beer goes cloudy when small quantities of

heavy metals are released by corrosion).

6. Perforation of vessels and pipes allowing escape of their contents and possible harm to the

surroundings. For example a leaky domestic radiator can cause expensive damage to carpets and

decorations, while corrosive sea water may enter the boilers of a power station if the condenser

tubes perforate.

37
7. Loss of technically important surface properties of a metallic component. These could include

frictional and bearing properties, ease of fluid flow over a pipe surface, electrical conductivity of

contacts, surface reflectivity or heat transfer across a surface.

8. Mechanical damage to valves, pumps, etc., or blockage of pipes by solid corrosion products.

9. Added complexity and expense of equipment which needs to be designed to withstand a

certain amount of corrosion, and to allow corroded components to be conveniently replaced.

(Mohd, n.d)

2.5 Prevention Of Corrosion

For corrosion to take place, three conditions must be met. Availability of a metallic surface,

presence of moisture and an electron acceptor. If any of these conditions is removed, corrosion

will be inhibited. .

There are four common methods used to prevent corrosion. These methods include:

1. Cathodic protection

2. Protective coatings and linings.

3. Material selection.

4. The use of corrosion inhibitors

2.5.1 Cathodic Protection

Cathodic protection (CP) is a technique used to control the corrosion of a metal surface by

making it the cathode of an electrochemical cell. A simple method of protection connects the

metal to be protected to a more easily corroded “sacrificial metal “to act as the anode. The

sacrificial metal then corrodes instead of the protected metal. For structures such as long

38
pipelines, where passive galvanic cathodic protection is not adequate, an external DC electrical

power source is used to provide sufficient current. Cathodic protection systems protect a wide

range of metallic structures in various environments. Common applications are: steel water or

fuel pipelines and steel storage tanks such as home water heaters ; steel pier piles; ship and boat

hulls; offshore oil platforms and onshore oil well casings; offshore wind farm foundations and

metal reinforcement bars in concrete buildings and structures. Another common application is in

galvanized steel, in which a sacrificial coating of zinc on steel parts protects them from rust.

Cathodic protection can, in some cases, prevent stress corrosion cracking. (Ashworth, 1994).

2.5.2 Protective Coating and Linings

A coating is a covering that is applied to the surface of an object, usually referred to as the

substrate. The purpose of applying the coating may be decorative, functional, or both. The

coating itself may be an all-over coating, completely covering the substrate, or it may only cover

parts of the substrate. An example of all of these types of coating is a product label on many

drinks bottles- one side has an all-over functional coating (the adhesive) and the other side has

one or more decorative coatings in an appropriate pattern (the printing) to form the words and

images. Paints and lacquers are coatings that mostly have dual uses of protecting the substrate

and being decorative, although some artists‟ paints are only for decoration, and the paint on large

industrial pipes is presumably only for the function of preventing corrosion.

This is the most commonly specified lining material in today‟s water transmission industry. A

lean mixture of three parts sand to one part cement is centrifugally spun onto the interior surface

to create a dense, smooth surface.(Fristed, 2000).

39
The actual cement application is performed by pumping or pouring a high slump cement mixture

onto a slowly rotating length of pipe. The rotating speed is then increased so the proper

centrifugal forces level out the wet mortar to a uniform thickness. Continuous spinning removes

the excess water and compacts the mixture to a dense and hard surface. After the spinning

process, the lining is cured either by moist curing at ambient temperature or by an accelerated

process using steam. Other examples of coatings includes: drying oils and vanishes, synthetic

clear coatings, etc.

Like concrete, cement-mortar lining can develop drying cracks, but these cracks will self-heal

when the lining is wet. Wetting the cement lining also causes the lining to swell thereby

increasing strength and adherence.Bonded dielectric linings have been used as protective linings

for above-ground applications for many years. Epoxies and polyurethane-based products are two

major categories of liquid film linings used in the waterworks industry. These linings have

excellent water and chemical resistance properties and can be used as an alternative to cement

mortar lining.

Cement Mortar Coating works by chemically inhibiting corrosion. The cement creates a highly

alkaline environment at the interface of the pipe surface. Steel pipe, when protected by this high-

alkaline environment, will exhibit no corrosion or corrosion at a reduced rate. One disadvantage

with this is that soils with high concentrations of chlorides or sulfates may adversely affect

cement mortar coating protective properties.

Cement-mortar coating, although consisting of the same mixture as cement lining, is applied at a

very low moisture content, or „no slump‟ consistency. (Northwest Pipe Company, n.d).

40
2.5.3 Material Selection

The fundamental resistance of stainless steel to corrosion occurs because of its ability to form an

oxide protective coating on its surface. This thin coating is invisible, but generally protects the

steel in oxidizing environments (air and nitric acid). However, this film loses its protectiveness in

environments such as hydrochloric acid and chlorides. In stainless steels, lack of oxygen also

ruins the corrosion protective oxide film, therefore these debris ridden or stagnant regions are

susceptible to corrosion. (Mohd, n.d)

Nickel alloys provide good resistance to a wide range of corrosive environment. They have the

basic corrosion resistance of nickel combined with the added resistance associated with the

alloyed metal. Alloy 400 (67Ni-33Cu) has good resistance at ambient temperatures to most of

the nonoxidizing acids, such as hydrofluoric, sulphuric, and phosphoric acids. It also resists

nonoxidizing salts. Also, in alloy C-276 (54Ni-16Mo-16Cr), chromium and molybdenum are

added to nickel to improve the alloy‟s resistance to oxidizing conditions. Both alloy-400 and

alloy C-276 have excellent corrosion resistance against atmospheric conditions and fresh water.

Alloy C-276 is resistant to stagnant seawater.

Another material that is able to withstand corrosion due to influence of acid is tantalum. It is a

useful material in corrosive applications involving hydrochloric acid and acidic ferric chloride

solutions. In general, tantalum has good resistance to hydroiodic, hydrobomic, boiling

hydrochloric, nitric, phosphoric, and sulfuric acids. Although, this material is affected by

hydrofluoric acid, hot fuming furic acid and fluorine. It is also attacked by alkaline solutions.

Nickel-plated carbon steel is an effective means for giving metal surfaces a corrosion resistant

coating. It has good resistance to the milder forms of atmospheric conditions, to oxidation, to

higher temperatures, and to halogen gases.(Mohd, n.d)

41
Gold-plated materials also prevent corrosion. Placing a thin layer of gold to a base metal will

provide protection against hydrogen permeation. Gold plating is suggested in applications where

atomic hydrogen is present.

2.5.4 Corrosion inhibitor

Among the numerous methods to avoid or prevent destructive or degradation of metal surface,

the corrosion inhibitor is one of the best known methods of corrosion protection and one of the

most useful in the industry. Inhibitors are substances or mixtures that in low concentration and in

aggressive environment inhibit, prevent or minimize the corrosion of metals. Generally, the

mechanism of the inhibitor is one or more of three that are cited below:

 The inhibitor is chemically adsorbed on the surface of the metal and this forms a protective

thin film with inhibitor effect or by combination between inhibitor ions and metallic surface.

 The inhibitor leads a formation of a film by oxide protection of the base metal

 The inhibitor reacts with a potential corrosive component present in aqueous media and the

product is a complex.

Corrosion inhibitors can either be a synthetic or natural chemical. They are classified by:

 The chemical nature as organic or inorganic

 The mechanism of action as anodic, cathodic or a anodic-cathodic mix and by adsorption

action.

 As oxidants or not oxidants.

42
Generally, synthetic inhibitors have cathodic actions or anodic. The natural inhibitor has both

actions, cathodic and anodic and the protective by a film adsorption.

Anodic inhibitors: They are also known as passivation inhibitors. They act by reducing anodic

reaction that is, blocking the anodic reaction and supporting the natural reaction of passivation

metal surface. The inhibitors react with the corrosion product, initially formed, resulting in a

cohesive and insoluble film on the metal surface. For the anodic inhibitor to be effective, it is

very important that the inhibitor concentrations be high enough in the solution. When the

concentration is not enough, it affects the formation of film protection, because it will not cover

the metal completely, leaving the sites of the metal exposed, thus causing a localized corrosion.

Examples of anodic inorganic inhibitors are nitrates, molybdates, sodium chromates, phosphates,

hydroxides and silicates

Cathodic inhibitors: They prevent the occurrence of the cathodic reaction of the metal. These

chemicals have metal ions able to produce a cathodic reaction due to alkalinity, thus producing

insoluble compounds that precipitate selectively on cathodic sites. The cathodic inhibitors form a

barrier of insoluble precipitates over the metal, covering it. Thus, this restricts the metal contact

with the environment, even when it is completely immersed. Because of this, cathodic inhibitors

are independent of concentrations. This makes them better than anodic inhibitors. Some

examples of cathodic inhibitors include: Mg (OH)2, Zn(OH)2, Ni(OH)2. These are deposited on

the cathodic site of the metal surface, thereby protecting it.

Organic inhibitor: Organic compounds used as inhibitors can either act as an anodic inhibitor or

a cathodic inhibitor. They can as well act as both. But either way, this inhibitors act through a

process of surface adsorption, known as film-forming. They build up a protective hydrophobic

43
film adsorbed molecules on the surface of the metal, which provides a barrier to the dissolution

of the metal in the electrolyte. The efficiency of an organic inhibitor depends on the:

 Chemical structure, like the size of the organic molecule.

 Aromaticity and/or conjugated bonding, as the carbon chain length.

 Type and number of bonding atoms or groups in the molecule

 Nature and the charges of the metal surface of adsorption mode like bonding strength to

metal substrate

 Ability for a layer to become compact or cross-linked.

 Capability to form a complex with the atom as a solid within the metal lattice

 Type of the electrolyte solution like adequate solubility in the environment.

Organic inhibitors that contain oxygen, nitrogen and sulfur are adsorbed on the metallic surface

blocking the active corrosion sites. The most effective and efficient organic inhibitors are

compounds that have pi-bonds, it present biological toxicity and environmental harmful

characteristics. Some examples are amines, urea, mercaptobenzothiazole (MBT), benzotriazole e

toliotriazol, aldehydes, heterocyclic nitrogen compounds, sulfur-containing compounds and

acetylenic compounds and also ascorbic acid, succinic acid, tryptamine, caffeine and extracts of

natural substances. (Camila et al, 2014).

2.6 Corrosion Monitoring

The field of corrosion measurement, control, and prevention covers a very broad spectrum of

technical activities. Within the sphere of corrosion control and prevention, there are technical

44
options such as cathodic and anodic protection, materials selection, chemical dosing and the

application of internal and external coatings. Corrosion measurement employs a variety of

techniques to determine how corrosive the environment is and at what rate metal loss is being

experienced. Corrosion measurement is the quantitative method by which the effectiveness of

corrosion control and prevention techniques can be evaluated and provides the feedback to

enable corrosion control and prevention methods to be optimized.

2.6.1 Corrosion Techniques

A large number of corrosion monitoring techniques exist. The following list details the most

common techniques which are used in industrial applications:

 Corrosion Coupons (weight loss measurements)

 Electrical Resistance (ER)

 Linear Polarization Resistance (LPR)

 Galvanic (ZRA)

 Hydrogen Penetration

 Microbial

 Sand/Erosion

These corrosion monitoring techniques have been successfully applied and are used in an

increasing range of applications because:

 The techniques are easy to understand and implement.

 Equipment reliability has been demonstrated in the field environment over many years of

operational application.

45
 Results are easy to interpret.

 Measuring equipment can be made intrinsically safe for hazardous area operation.

 Users have experienced significant economic benefit through reduced plant down time and

plant life extension.

Corrosion Coupons (Weight Loss)

The Weight Loss technique is the best known

and simplest of all corrosion monitoring

techniques. The method involves exposing a

specimen of material (the coupon) to a process

environment for a given duration, then removing

the specimen for analysis. The basic Figure 6: metal coupons

measurement which is determined from corrosion coupons is weight loss; the weight loss taking

place over the period of exposure being expressed as corrosion rate.The simplicity of the

measurement offered by the corrosion coupon is such that the coupon technique forms the

baseline method of measurement in many corrosion monitoring programs.

Advantages of weight loss coupons are that:

• The technique is applicable to all environments - gases, liquids, solids/particulate flow.

• Visual inspection can be undertaken.

• Corrosion deposits can be observed and analyzed.

• Weight loss can be readily determined and corrosion rate easily calculated.

• Localized corrosion can be identified and measured.

• Inhibitor performance can be easily assessed

46
In a typical monitoring program, coupons are exposed for 90-day duration before being removed

for a laboratory analysis. This gives basic corrosion rate measurements at a frequency of four

times per year. The weight loss resulting from any single coupon exposure yields the “average”

value of corrosion occurring during that exposure. The disadvantage of the coupon technique is

that, if a corrosion upset occurs during the period of exposure, the coupon alone will not be able

to identify the time of occurrence of the upset, and depending upon the peak value of the upset

and its duration, may not even register a statistically significant increased weight loss.

Therefore, coupon monitoring is most useful in environments where corrosion rates do not

significantly change over long time periods. However, they can provide a useful correlation with

other techniques such as ER and LPR measurements.(Rosario, 2009).

Electrical Resistance (ER) Monitoring

ER probes can be thought of as “electronic” corrosion coupons. Like coupons, ER probes

provide a basic measurement of metal loss, but unlike coupons, the value of metal loss can be

measured at any time, as frequently as required, while the probe is in-situ and permanently

exposed to the process stream.

In this diagram, a standard ER instrument is

connected to a 40 mil wire loop element which

has a useful life of 10 mils. The instrument still

reads close to zero because the element is new.

Here the instrument reads around half-scale,

Figure 7: A standard ER instrument 47

indicating that the element has experienced about 5 mils of metal loss or about half of its useful

life. The instrument‟s reading is increasing proportionally with the resistance of the element,

which increases as a result of metal loss.

Here the instrument reads almost full scale, indicating that the element has experienced 10 mils

of metal loss and requires replacement.

The ER technique measures the change in Ohmic resistance of a corroding metal element

exposed to the process stream. The action of corrosion on the surface of the element produces a

decrease in its cross-sectional area with a corresponding increase in its electrical resistance. The

increase in resistance can be related directly to metal loss and the metal loss as a function of time

is by definition the corrosion rate. Although still a time averaged technique, the response time for

ER monitoring is far shorter than that for weight loss coupons.

ER probes have all the advantages of coupons, plus:

• Direct corrosion rates can be obtained.

• Probe remains installed in-line until operational life has been exhausted.

• They respond quickly to corrosion upsets and can be used to trigger an alarm.

Linear Polarization Resistance (LPR) Monitoring

The LPR technique is based on complex electro-chemical theory. For purposes of industrial mea-

surement applications it is simplified to a very basic concept. In fundamental terms, a small

voltage (or polarization potential) is applied to an electrode in solution. The current needed to

maintain a specific voltage shift (typically 10 mV) is directly related to the corrosion on the

surface of the electrode in the solution. By measuring the current, a corrosion rate can be

derived.

48
The advantage of the LPR technique is that the measurement of corrosion rate is made instanta-

neously. This is a more powerful tool than either coupons or ER where the fundamental measure-

ment is metal loss and where some period of exposure is required to determine corrosion rate.

The disadvantage to the LPR technique is that it can only be successfully performed in relatively

clean aqueous electrolytic environments. LPR will not work in gases or water/oil emulsions

where fouling of the electrodes will prevent measurements being made.

Galvanic Monitoring

The galvanic monitoring technique, also known as Zero Resistance Ammetry (ZRA) is another

electrochemical measuring technique. With ZRA probes, two electrodes of dissimilar metals are

exposed to the process fluid. When immersed in solution, a natural voltage (potential) difference

exits between the electrodes. The current generated due to this potential difference relates to the

rate of corrosion which is occurring on the more active of the electrode couple.

Galvanic monitoring is applicable to the following electrode couples:

• Bimetallic corrosion

• Crevice and pitting attack

• Corrosion assisted cracking

• Corrosion by highly oxidizing species

• Weld decay

Galvanic current measurement has found its widest applications in water injection systems where

dissolved oxygen concentrations are a primary concern. Oxygen leaking into such systems great-

ly increases galvanic currents and thus the corrosion rate of steel process components. Galvanic

49
monitoring systems are used to provide an indication that oxygen may be invading injection

waters through leaking gaskets or deaeration systems.(Rosario, 2009)

Hydrogen Penetration Monitoring

In acidic process environments, hydrogen is a by-product of the corrosion reaction. Hydrogen

generated in such a reaction can be absorbed by steel particularly when traces of sulphide or

cyanide are present. This may lead to hydrogen induced failure by one or more of several

mechanisms. The concept of hydrogen probes is to detect the amount of hydrogen permeating

through the steel by mechanical or electrochemical measurement and to use this as a qualitative

indication of corrosion rate.

Biological Monitoring

Biological monitoring and analysis generally seeks to

identify the presence of Sulphate Reducing Bacteria - SRB‟s.

This is a class of anaerobic bacteria which consume sulphate

from the process stream and generate sulphuric acid, a

Figure 8
corrosive which attacks production plant materials.

Sand / Erosion Monitoring

These are devices which are designed to measure erosion in a flowing system. They find wide

application in oil/gas production systems where particulate matter is present.(Rosario, 2009).

50
2.6.2 Applications of Corrosion Monitoring Techniques

Corrosion monitoring is typically used in the following situations:

 Where risks are high - high pressure, high temperature, flammable, explosive, toxic

processes.

 Where process upsets can cause high corrosivity.

 Where changes in operating conditions can cause significant changes in corrosion rate.

 Where corrosion inhibitors are in use.

 In batch processes, where corrosive constituents are concentrated due to repeated cycling.

 Where process feedstock is changed.

 Where plant output or operating parameters are changed from design specifications.

 In the evaluation of corrosion behavior of various alloys.

 Where induced potential shifts are used to protect systems and/or structures.

 Where product contamination due to corrosion is a vital concern.

2.7 Review of Related Works

Numerous works have been carried out in the time past by researchers, experts in determining

ways of reducing the rate of corrosion of different metals and alloys. The researches cut across

the different forms of corrosion, environments and materials. Brief descriptions of some of the

published articles are given below.

Landolfo (2010) carried out a research on the modeling of metal structure corrosion damage. In

his work, he presented different modeling approaches to atmospheric corrosion. He classified

51
corrosiveness into five (5) categories, from C1 to C5. Respectively, this category includes: very

low, low, medium, high and very high. These categories are illustrated in different outdoor

atmospheric environments. For the C1 category, the typical environment is dry and cold zones

e.g. desert. The C2 category, the typical environment is the temperature zone; it is categorized

with low pollution. In the C3 category, there is presence of low chloride influences, including the

C4 category. The C5 category is characterized with high pollution levels. From his work, he

found out that the largest part of corrosion models are calibrated on the basis of local field test

exposure data. Since the empirical coefficients that characterize each model are strongly

influenced by the exposure location, condition and duration, such models can be used for similar

environmental conditions. The model he used in his work was that of Klinesmith‟s corrosion

model. This model provides an average thickness loss of about 1.7mmfor a design life of 50

years, which is approximately 10-times more than the precisions given by the other models.

Nyborg (2010) wrote a piece of work, giving an overview of the different prediction models used

in the oil and gas industry for evaluation of Co2 corrosion of carbon steel. In his work, it was

understood that the major differences in the models were in how they predict the effect of

protective corrosion films and the effect of oil wetting on CO2 corrosion. The model includes:

De waard model, Norsok M-506 model, Hydrocor, Corplus, Cassandra, KSC model, Multicop,

ECE model, Predict, Tulsa model, ULL model, CorPos, OLI model, SweetCor. He also went

further in highlighting some important factors for predicting CO2 Corrosion. These factors

includes: determination of pH, effect of organic acids, effects of protective corrosion films,

effects of oil wetting, effect of H2S and connection with multiphase flow properties.

Mohebbi et al (2011) carried out an experimental investigation on corrosion of cast iron pipes.

Although, many studies have been carried out to determine the corrosion behavior of cast iron,

52
little research had been undertaken to understand how cast iron pipes behave over a longer time

scale hours, days or weeks. Hence, their work was centered on investigating the corrosion

behavior of cast iron over a long period of time. In their research, the behavior of three (3)

eservice pipes was thoroughly investigated in three (3) simulated service environments.

The specimens (35mm x 25mm) were cut from the eservice water mains, washed with 50%

acetone, dried and weighed prior to the exposure to the test environment. The first set of

experiment was the scenario where a pipe was exposed to static water. The second and third

pipes were laid in aerated and corrosive environment respectively, and constantly being washed

by flowing water.

From their results, it was observed that localized corrosion is the primary form of corrosion in

cast iron water pipes. They also found out that the micro structural features (ferrite, pearlite and

graphite flakes) of cast irons is a key factor that affects the corrosion behavior of cast iron pipes.

They also investigated the corrosion products of cast irons and determined the corrosion rate.

More so, the long term corrosion properties of the pipes were characterized. It was observed that

the corrosion rate of grey cast iron pipes in aqueous environment can range between 0.1-

0.7mm/year depending on the oxygen level and the corrosiveness of the environment.

Nguyen et al (2012) researched on the climate change impacts on corrosion of metal fasteners

and their zinc coating in timber construction. Potential impacts of climate change, including

changes in temperature, relative humidity, and wind speed were modeled and incorporated into

an Australian atmospheric corrosion model developed for the exposed parts of fasteners.

The model predicts the atmospheric corrosion rates of structural steel fasteners and related zinc

coatings. The data used for derived from small exposed coupons of steel and zinc.

53
For engineering applications in Australia, it was proposed that in the absence of pollution, the

mean atmospheric corrosion rate of zinc could be estimated from

Co,z = 0.025t0.6s0.5

Where, t is the time of surface wetness per year (%)

S is the airborne salinity in mg/m2/day

For the computation of t and S, many input parameters were required. Some of these parameters

includes: the hazard zone, local climate factors, the distance from the coast, the coastal exposure,

etc.

The rate of corrosion was computed from the model, and it was discovered that the corrosion rate

attenuates rapidly with distance from the coast.

Models were also generated on the effects of wind speed on airborne salinity, effects of

temperature on corrosion rate, and the effects of relative humidity on time of wetness.

Ofoeyeno et al (2014) performed an analytical modeling of pipeline failure in multiphase flow

due to corrosion in Niger Delta region. In their work, the role that velocity, density, water cut

and other parameters play in predicting corrosion was analyzed with Norsok Model. At the end

of the research, the result showed that velocity played a key role in corrosion prediction. Also, by

increasing the velocity of oil from 0.1 to 1.25 m/s, there would be a corresponding increase of

corrosion rate from 1.67 to 5.58mm/yr. The reason being that at the selected pH of 4, the

corrosion rate is very sensitive to mass transfer and turbulent mixing which are in turn increased

when the flow rates are increased. The Norsok model used was able to take into account the

54
effect of protective corrosion films and was able to predict lower corrosion rates at high

temperature and high pH. This is unlike the Waard model.

Velazquez et al (2014) carried out a statistical modeling of pitting corrosion. As stated earlier,

pitting corrosion is one of the main threats that affects the durability of vessels and pipeline

steels that transport crude or hydrocarbon. In generating their model, these experts used two

stochastic models in their methodology. The first being a Poisson process, was used to model the

pit initiation while the second, gamma process was used to model the pit depth-growth. Data

gotten from experiments was used to construct plots, from which it was discovered that for

longer times, the pits initiated on the metal surface continue growing.

A model on the corrosion behavior of iron in an acidic medium was developed by Abdelhadi et

al (2010). The metal was subjected to an aerated 0.1N HCl, at various temperatures and speed of

agitation. The data realized was analyzed using ANOVA and MATLAB. The model generated

was:

CR (mm/y) = 90.85 – 5.02 x 10-3TS + 4.08 x 10-4T3 +2.3 x 10-7T2S2 – 10-9T3S2

Where, T is time

S is speed of agitation

The model was chosen according to the highest R2 based on T-test with 95% confidence limit.

The speed of agitation used was: stagnant, 300 and 900 RPM, while the temperatures were 30,

45 and 60oC. The results revealed that the model is significant according to ANOVA statistical

analysis based on F and P-tests. Nine different experiments with at least two representative runs

for the same condition were conducted, the average values of corrosion rates then taken. From

the result, it was shown that the speed of agitation played the role of an erosion factor in

55
destroying the oxide film and as a result, increasing the rate of corrosion. Also, from the

experiment, it was discovered that as the temperature of the medium increased, the rate of

corrosion also increased.

Wang et al (2014) developed a cover cracking model in reinforced concrete structures subject to

rebar corrosion. For more understanding, rebar corrosion involves rust, which contributes to an

expansive radial pressure at the concrete-steel interface and hoop tensile stresses in the

surrounding concrete. Once the stress state exceeds a certain limit, anisotropic damage occurs.

These experts established an anisotropic damage model for concrete, then an analytical model to

calculate the displacement and the stress in a corroded reinforced concrete structural member

based on that anisotropic damage.

In their work, they explained that when a rebar corrodes, it produces corrosion products (rust)

which will expand. Because corrosion rusts take a greater volume than virgin steel bar, they can‟t

expand freely. Hence, they bring about expansive force to the concrete cover. This expansive

force brings about anisotropic damage resulting to micro-cracks near a rebar.

Models were proposed in describing the volumes of the generated rust and that of the steel

consumed. These experts also went further to develop mathematical equations governing

concrete-rust-steel composite, elastic strain-displacement relation, stress-strain relations and

many more. They also tested the proposed model using a specimen with the dimension 100mm x

100mm x 100mm. The concrete was cast with Portland cement. A longitudinal rebar was

embedded inside the specimen. Plots were made and was discovered that the predicted values

matched the experimental data that were acquired every 10mins.

56
Dhawan et al (2015) carried out a research work to determine the slurry erosion behavior of

stainless steel under certain parameters. These parameters were: the effect of slurry concentration

(ppm), average size of slurry particles and rotational speed. Erosion corrosion is usually noticed

in hydro turbine steels, most especially hydro power plants that are situated on the rivers. In

carrying out their experiment, stainless steel grade-316 was selected because it the major

material in making hydro-turbines.

More so, for bringing the testing conditions as close as possible to the actual hydropower plants,

the sand particles used as erodent were of silica sand. A high-speed test rig (DUCOM TR401)

was used to study the erosion behavior of the steel. Before the start of the experiment, initial

weight of the specimen was taken. Subsequently, after every 15mins, the final weights were

taken with the help of a precision microbalance having an accuracy of 0.1mg. The specific mass

loss was determined from the equation:

Specific mass loss = mass loss (g) x 106/ peripheral surface area (m2)

In determining the effect of the chosen parameters, the experts made use of Taguchi

methodology. The results were plotted graphically. For each experiment, two graphs were

plotted. They were: cumulative specific weight loss in g/m2 against time and cumulative specific

weight loss rate in g/m2-min against time in minutes.

From their analysis and graphical representation, they came to the conclusion that by increasing

the speed of rotation and erodent size, the rate of erosion of the stainless steel grade-316

increased. But by increasing the concentration of slurry, they realized that the erosion of the steel

decreased. But further increment in the concentration resulted to an increase in the erosion of the

specimen.

57
Falcon et al (2015) wrote a research article titled: Dodecylamine-Loaded Halloysite

Nanocontainers for Active Anticorrosion Coatings.Currently, the most promising approach in the

corrosion protection of smart coatings is the use of nanoreservoirs loaded with corrosion

inhibitors. Nanocontainers are filled with anti-corrosive agents and are embedded into a primer

coating. Future prospective containers are halloysite nanotubes (HNTs) due to their low price,

availability, durability, with high mechanical strength and biocompatibility. The aim of their

work was to study the use of HNTs as Nanocontainers for encapsulated Dodecylamine for active

corrosion protection of carbon steel.Halloysite clay was characterized by X-ray diffraction and

TGA – thermogravimetric analysis techniques. HNTs were loaded with Dodecylamine and were

embedded into an alkyd primer with a weight ratio of 10 wt. %. The anti-corrosiveperformance

of the alkyd primerdoped with 10 wt. % of entrapped-Dodecylamine halloysite was tested

oncoated carbon steel by direct exposureof the coated samples with aprovoked defect into 0.01

mol/L NaClcorrosive media using electrochemicalimpedance spectroscopy (EIS) andscanning

vibrating electrodetechnique (SVET). EIS and SVETmeasurements showed the self-healing

properties of the doped alkydcoating. Coated samples were alsoevaluated in a salt spray

chamberand the self-healing effect wasunequivocally noticed.

The XRD studies showed that the halloysite sample contained other types of minerals as alunite,

quartz,kaolinite, and gibbsite, which mayhave affected the performance of

thehalloysite.Thermogravimetric curves indicatedmore than one simple step for therelease and/or

degradation ofdodecylamine from halloysitestructure. It was possible to estimatethe amount of

inhibitor loaded in thehalloysite nanoclay.Electrochemical impedancespectroscopy and SVET

results for thecarbon steel coated with a primerlayer doped with 10 wt. % of HNTsloaded with

dodecylamine inhibitorshowed self-healing ability by releaseof the encapsulated

58
inhibitortriggered by pH changes aroundprovoked defect inhibiting thekinetics of corrosion

process.The salt spray tests showed that theaddition of dodecylamine-loadedHNTs on the primer

of coated samplesprovided self-healing properties, withthe release of inhibitor from thelumen of

halloysite inhibiting theattack provoked by the corrosionprocess.These results unquestionably

provedthe self-healing capacity of the alkydprimer doped with halloysite loadedwith

dodecylamine and prescribes thepossibility of enhancing the protectiveproperties of such coating

system thatis well known as not the best for highperformance coatings.

Lutz et al (2016) carried out a research and wrote an article titled “A multiple-Action self-

Healing Coating”. Their work described a self-healing coating for corrosion protection of metals,

which combines two different types of self-healing mechanisms in one coating with multiple-

healing functionality.In their article, it was discovered that many researchers are trying to tackle

the immanent problem of corrosion by using self-healing coatings for all kinds of applications

(off-shore wind parks, airplanes, airplanes, automotive industry, chromium replacement, etc.).

The researchers works have led to different sorts of self-healing mechanisms being developed,

which fulfill different requirements. Some of the latest advances in the field includes: existence

of coatings that physically close or fill defects, coatings that automatically protect the metal

substrate underneath the coating against corrosion induced by aggressive species.

Alternatively, from their work, it was concluded that self-healing coatings are in two categories:

intrinsically healing coatings where the coating matrix performs the healing and extrinsically

healing coatings that embody containers within the coating matrix that release a healing agent.

The categorization was also termed autonomous and non-autonomous/on-demand self-healing

coatings. For the autonomous, the coatings tend to carry out their intended function when

triggered by the corrosion process itself or the infliction of a defect. For the non-autonomous, the

59
self-healing mechanism is triggered by heat. From the works of these researchers, it was

discovered that the self-healing mechanism not only has its advantages but also has its

disadvantages. Because of the disadvantages associated with it, Lutz and other experts developed

a multi-action self-healing (MASH) coating that combines an extrinsic autonomous corrosion

protection system with an intrinsic on-demand shape-recovery coating. 2-mercaptobenzothiazole

(MBT) was loaded into layered double hydroxide (LDH) carriers that were mixed into an

acrylated polycaprolactone polyurethane-based shape-recovery coating and applied on hot-dip

galvanized steel. Electrochemical impedance spectroscopy and scanning vibrating electrode

technique demonstrated the corrosion protection effect of MBT in the coating with a defect and

the restoration of the barrier properties of the coating after defect closure.

60
 CHAPTER THREE
Methodology
3.1 Experimental Methodology

Two variables (concentration and time) were studied in this work.

3.1.1Materials and equipment:

 Specimen

10 pieces of rectangular mild steels (less than 0.25 percent carbon) with equal dimensions

(length: 8cm, width: 3cm and thickness: 0.1cm) were used.

 Electrolyte

The electrolyte used in this work was different salt concentrations of 31ppt, 33ppt, 35ppt,

37ppt and 39ppt. Distilled water was used in making the salt solutions

 Magnetic stirrer to homogenize the salt solution

 Analytical weighing balance

 1000mls beakers

 Acetone

 Pieces of wood.

 Abrasive paper

61
3.1.2 Procedure:

The rectangular cut mild steels were finished with abrasive paper to remove dirt and rust

from them. A hole was drilled on each of them to enable the metal to be tied to a wood

with a thread. This was to enable the metal to be submerged into the solution without

touching the bottom or sides of the beaker.

Before being inserted into the salt solutions, the mild steels were washed thoroughly with

distilled water, and then cleaned with acetone to remove grease stains or oil marks. After

this, they were air dried and then immediately weighed in the analytical balance before

being dipped into the salt solutions. These solutions were properly labeled with their

corresponding mild steels. This was to avoid mix up. It should be noted that the salt water

used for this experiment was a simple solution of table salt (NaCl) and water

The mild steels were left in the

solution for a period of five (5)

weeks (168hours). On the seventh

(7th) day of each week, the mild

steels were removed from their

solutions, washed in running water

with the aid of a bristle brush.

It was then dipped into acetone,

air dried and weighed. Vigorous Figure 8: mild steel coupon inserted into salt water solution

62
cleaning was avoided because it might end up removing the base metal. This treatment on

the mild steels before dipping and after removal for reweighing is according to ASTM

standard

The experiment was carried out at room temperature of 27oC.

Magnetic Stirrer Analytical Weighing balance 1000mls beaker

Tough abrasive paper Mild Steel

63
3.1.3 Measurement of weight loss and corrosion rate determination:

The weight loss of each week was obtained using the weighing balance. The difference in

the weight of the mild steels was obtained by subtracting the present weight from the

weight obtained before dipping into the solution for that week.

The most common method for determining a corrosion rate from mass loss is to weigh

the corroding sample before and after exposure and divide by the total surface area and

the total exposed time. The corrosion rate is measured in mm/year. The formula for

determining corrosion rate is given as:

CR = K x W
AxTxP

Where CR means corrosion rate in mm/yr.

W means weight loss in gram

A means exposed surface area of the coupon (24cm2)

P means the density of the mild steel (7.86g/cm3)

K means constant for unit conversion.

3.2 Mathematical methodology

The values of concentration would be plotted against time in hours. With these plots, it

would be determined if the corrosion reaction follows a zero order, first order or second

order reaction.

64
 Zero order reactions:

A reaction is of zero order when the rate of reaction is independent of the concentration

of materials.

-rA= - dCA= K (3.1)

dt

For a zero order reaction, the plot is of this form:

 First order reaction

A B

For first order reaction, the plot is of this form:

65
 Second order reaction

A+B S+R

For a second order reaction, the plot is of the form:

In addition, from the five different plots, it would be determined if the order of reaction

changes as concentration changes or constant for varying corrosion rates.

For better results, matlab software would be used to obtain a surface plot showing the

interaction between concentration and time. More so, with the help of the curve fitting

toolbox (a feature in matlab), the best model would be obtained with the best value of R 2,

and a 95 percent or more confidence limit.

The model to be generated by the matlab software could be linear, interactive, purely

quadratic or quadratic.

66
 CHAPTER FOUR

RESULT ANALYSIS

The results shown are an illustration of the changes in mass of each metal or coupon as they

corroded. Analysis was taken in a period of 168 hours interval for 840 hours (5 weeks). As the

corrosion proceeded, it was observed that there were physical changes on the metal surfaces

which showed the effect of salt solution on the mild steel. After each week, it was observed that

the metal has corroded to a certain extent leaving behind metallic deposits in the solution and the

formation of dark brown metallic surface. This effect continued, but reduced as the number of

hours increased. The initial weight of the metal and the final weight after the metal had corroded,

at each interval was recorded as shown below.

Table 4.1a Mass of mild steel before and after corrosion at 31g-salt/L-water

TIME MASS AT 1ST MASS AT 2ND MASS AT 3RD AVERAGE

(HOURS) EXPERIMENT EXPERIMENT EXPERIMENT MASS

0 20.201 20.201 20.201 20.201

168 20.127 20.126 20.125 20.126

336 20.070 20.071 20.072 20.071

504 19.989 19.988 19.990 19.989

672 19.935 19.937 19.936 19.936

840 19.860 19.862 19.861 19.861

67
Chemistry of reaction: 4Fe (s) + 3O2 (g) + 6H2O (l) 4Fe (OH) 3(s)

Assume first order;

Where n = 1

∫ ∫

( )

Since we are working in terms of mass, therefore let

Where M = mass weighed after each week interval, the formula then becomes

At 31g-salt/L-water, the initial mass = 20.201grams

68
And mass after 5 weeks, = 19.861

We then find the value of k using the formula;

In( )

In( )

And K = 2.021

We then use curve fitting tool on MATLAB (matrix laboratory) to fit our data to obtain a good

fit. The figure shown below is a cropped copy of the MATLAB results.

Figure 4.1: MATLAB results at 31g-Salt/L-Water

69
From the information in the figure above, we then ascertain the goodness of the fit with the

following parameters.

Table 4.1b: Values showing the goodness of fit

GOODNESS OF FIT VALUES

Sum of Squares due to Error (SSE) 0.0001854

R-square 0.9977

Adjusted R-square 0.9971

Root Mean Squared Error 0.006808

From the table shown above, it could be seen that the values for each criterion falls within the

range of accepted values. Hence, it is a good fit making it a first order reaction.

Table 4.2a: Mass of mild steel before and after corrosion at 33g-salt/L-water

TIME MASS AT 1ST MASS AT 2ND MASS AT 3RD AVERAGE

(HOURS) EXPERIMENT EXPERIMENT EXPERIMENT MASS

0 20.201 20.201 20.201 20.201

168 20.144 20.146 20.145 20.146

336 20.063 20.065 20.064 20.064

504 20.015 20.014 20.016 20.015

672 19.937 19.935 19.936 19.936

840 19.881 19.882 19.880 19.881

70
The following calculations were then carried out at concentration of 33g salt/L water.

At 33g-salt/L-water, the initial mass = 20.201grams

And mass after 5 weeks, = 19.881

We then find the value of k using the formula;

In( )

In( )

And K = 1.901

We then use curve fitting tool on MATLAB (matrix laboratory) to fit our data to obtain a good

fit. The figure shown below is a cropped copy of the MATLAB results.

From the information in the figure below, we then ascertain the goodness of the fit with the

following parameters.

71
Figure 4.2: MATLAB results at 33g-salt/L-water

Table 4.2b: Values showing the goodness of fit

GOODNESS OF FIT VALUES

Sum of Squares due to Error (SSE) 0.0002545

R-square 0.9966

Adjusted R-square 0.9957

Root Mean Squared Error 0.007977

From the table shown above, it could be seen that the values for each criterion falls within the

range of accepted values. Hence, it is a good fit making it a first order reaction.

72
Table 4.3a: Mass of mild steel before and after corrosion at 35g salt/L water

TIME MASS AT 1ST MASS AT 2ND MASS AT 3RD AVERAGE

(HOURS) EXPERIMENT EXPERIMENT EXPERIMENT MASS

0 20.201 20.201 20.201 20.201

168 20.142 20.141 20.143 20.142

336 20.066 20.067 20.068 20.067

504 20.019 20.021 20.020 20.020

672 19.946 19.947 19.945 19.946

840 19.888 19.890 19.889 19.889

The following calculations were then carried out at concentration of 35g-salt/L-water.

At 35g-salt/L-water, the initial mass = 20.201grams

And mass after 5 weeks, = 19.889

We then find the value of k using the formula;

In( )

In( )

73
And K = 1.853

We then use curve fitting tool on MATLAB (matrix laboratory) to fit our data to obtain a good

fit. The figure shown below is a cropped copy of the MATLAB results.

Figure 4.3: MATLAB results at 35g salt/L water

From the information in the figure below, we then ascertain the goodness of the fit with the

following parameters.

Table 4.3b: Values showing the goodness of fit

GOODNESS OF FIT VALUES

Sum of Squares due to Error (SSE) 0.0001564

R-square 0.9977

Adjusted R-square 0.9972

Root Mean Squared Error 0.006254

74
From the table shown above, it could be seen that the values for each criterion falls within the

range of accepted values. Hence, it is a good fit making it a first order reaction

Table 4.4a: Mass of mild steel before and after corrosion at 37g salt/L water

TIME MASS AT 1ST MASS AT 2ND MASS AT 3RD AVERAGE

(HOURS) EXPERIMENT EXPERIMENT EXPERIMENT MASS

0 20.201 20.201 20.201 20.201

168 20.142 20.144 20.143 20.143

336 20.106 20.107 20.105 20.106

504 20.059 20.060 20.061 20.060

672 19.995 19.994 19.996 19.995

840 19.950 19.951 19.949 19.950

The following calculations were then carried out at concentration of 37g salt/L water.

At 37g-salt/L-water, the initial mass = 20.201grams

And mass after 5 weeks, = 19.950

We then find the value of k using the formula;

75
In( )

In( )

And K = 1.488

We then use curve fitting tool on MATLAB (matrix laboratory) to fit our data to obtain a good

fit. The figure shown below is a cropped copy of the MATLAB results.

Figure 4.4: MATLAB results at 37g-salt/L-water

From the information in the figure above, we then ascertain the goodness of the fit with the

following parameters.

76
Table 4.4b: Values showing the goodness of fit

GOODNESS OF FIT VALUES

Sum of Squares due to Error (SSE) 0.0002105

R-square 0.9952

Adjusted R-square 0.994

Root Mean Squared Error 0.007254

From the table shown above, it could be seen that the values for each criterion falls within the

range of accepted values. Hence, it is a good fit making it a first order reaction

Table 4.5a: Mass of mild steel before and after corrosion at 39g salt/L water

TIME MASS AT 1ST MASS AT 2ND MASS AT 3RD AVERAGE

(HOURS) EXPERIMENT EXPERIMENT EXPERIMENT MASS

0 20.201 20.201 20.201 20.201

168 20.159 20.161 20.160 20.160

336 20.099 20.101 20.100 20.100

504 20.060 20.059 20.061 20.060

672 20.027 20.029 19.028 20.028

840 19.972 19.973 19.971 19.972

The following calculations were then carried out at concentration of 39g salt/L water.

At 39g-salt/L-water, the initial mass = 20.201grams

And mass after 5 weeks, = 19.889

77
We then find the value of k using the formula;

In( )

In( )

And K = 1.357

We then use curve fitting tool on MATLAB (matrix laboratory) to fit our data to obtain a good

fit. The figure shown below is a cropped copy of the MATLAB results.

From the information in the figure below, we then ascertain the goodness of the fit with the

following parameters.

Figure 4.5: MATLAB results at 39g-salt/L-water

Tab
le
4.5
b: Values showing the goodness of fit

78
 GOODNESS OF FIT VALUES

Sum of Squares due to Error (SSE) 0.0002105

R-square 0.9952

Adjusted R-square 0.994

Root Mean Squared Error 0.007254

From the table shown above, it could be seen that the values for each criterion falls within the

range of accepted values. Hence, it is a good fit making it a first order reaction

DETERMINATION OF CORROSION RATE

To determine the rate of corrosion for each of the salt concentrations, the underlying equation is

used. With this equation, one would be able to ascertain the effect of salt concentration on

corrosion rate.

 For 31g Salt/L Water;

K=2.021 x 10-5

=0.34g

A=2400mm2

T=840hrs

P=7.8 x 10-3g/mm3

Substituting into the equation we have;

79
 mm/hr

Converting to years,

 For 33g Salt/L Water;

K=1.901 x 10-5

=0.32g

A=2400mm2

T=840hrs

P = 7.8 x 10-3g/mm3

Substituting into the equation, we have:

mm/hr.

Converting to years,

 For 35g Salt/L Water;

K=1.853 x 10-5

=0.312g

A=2400mm2

80
 T=840hrs

P = 7.8 x 10-3g/mm3

Substituting into the equation, we have:

mm/hr.

Converting to years,

 For 37g Salt/L Water;

K=1.488 x 10-5

=0.251g

A=2400mm2

T=840hrs

P = 7.8 x 10-3g/mm3

Substituting into the equation, we have;

mm/hr.

Converting to years,

81
 For 39g Salt/L Water;

K=1.357 x 10-5

=0.229g

A=2400mm2

T=840hrs

P = 7.8 x 10-3g/mm3

Substituting into the equation, we have;

mm/hr.

Converting to years,

A summary of the effects of concentration on corrosion rate is shown in the figure below:

Table: 4.6

CONCENTRATION CORROSION RATE

31g Salt/L Water ⁄

33g Salt/L Water ⁄

35g Salt/L Water ⁄

37g Salt/L Water ⁄

39g Salt/L Water ⁄

82
 CHAPTER FIVE

CONCLUSION

In any redox reaction, metallic iron loses electrons to oxygen. The presence of salt in the water

accelerates the reaction because it increases the conductivity of water, thereby increasing the

concentrations of ions in the water. This leads to an increased rate of oxidation of the metal.

But the situation is made complicated by the fact that salt dissolved in water actually reduced the

amount of dissolved oxygen present in the water. This is because the water molecules are

attracted to the sodium and chloride ions, which has the tendency to decrease the weak affinity of

non-polar oxygen molecules to water, thereby driving oxygen away.

Hence, generally speaking, an increase in the concentration of salt molecules in a water medium

leads to a decrease in the amount of dissolved oxygen, which then reduces the rate of corrosion

and vice versa.

From the corrosion rates calculated for the different concentrations of salt solutions, it could be

seen that at 31g salt/L water, the corrosion rate was ⁄ , and at 39g salt/L

water, the corrosion rate was ⁄ ; showing a sharp decrease in the rate as a

result of a decrease in the concentration of dissolved oxygen in the medium.

As stated earlier, the average concentration of the sea water is 35g salt/L water. Being able to

determine a first order model and the rate of corrosion of mild steel based on the conditions by

which this experiment was subjected to, design and chemical engineers will be able to ascertain

when a particular structure placed on the sea is up for a change or not. It would also enable one

make good recommendations on the kind of structural material best for an engineering purpose.

83
 References

 Amani N. Abdelhadii, Ghaleb Y. Abbasi, Farqad, F.M. Saeed, (2010). Modeling and analysis

of the corrosion behavior of iron in aerated 0.1N HCl, at various temperatures and speed of

agitation using ANOVA and MATLAB. International Journal, Electrochemical Science, 5

(2010), 1665-1674.

 Ashworth V., (1994). Corrosion. Vol. 2, 3rd Edition.

 Ayo S. Afolabi, Tinyiko G, Ngwenya, Kazeem O. Sanusi and Ambali S. (2013). Stress

Corrosion Cracking of a Mild Steel in Orange Juice. Proceedings of the world congress on

engineering 2013 vol. 1, WCE 2013, London, U.K

 ASTM A262 Intergranular corrosion Testing of stainless steels.

 Alexander Lutz, Otto Van den Berg, Jan Wielant, Iris De Graeve and Herman Terryn,

(2016). A Multiple-Action Self-Healing Coating.

 Bill Nimmo, Gareth Hinds, (2003). Corrosion for beginners. Page 7

 Beech, I. Sunner, J, (2004). “Biocorrosion: Towards understanding interactions between

Biofilms and metals”. Current opinion in Biotechnology.

 Barbara A. Shaw, Robert G. Kelly, (2006). What is Corrosion?. The Electrochemical

Society.

 Camila G. Dariva, Alaxandre F. Galio, (2014). Corrosion Inhibitors- Principles, Mechanisms

and Applications.

 Edward Ghali, (2010). Corrosion resistance of aluminum and magnesium alloys.

 Fristad, W.E, (2000). Epoxy Coatings for Automotive Corrosion Protection.

84
 H. Mohebbi, C.Q. Li, (2011). Experimental Investigation on Corrosion of Cast Iron Pipes.

International Journal of Corrosion 2011, Article ID 506501, 17 pages.

 J.C. Velazquez, J.A.M. Van Der Weide, Enrique Hernandez, Hector Herrera Hernandez,

(2014). Statistical Modelling of Pitting Corrosion: Extrapolation of the Maximum Pit Depth-

Growth. International Journal, Electrochem.Sci. 9 (2014) 4129-4143.

 Jesus Marino Falcon, Tiago Sawczen and Idalina Vieira Aoki, (2015). Dodecylamine-Loaded

Halloysite Nanocontainers for Active Anticorrosion Coatings.

 Kathleen Rosario, (2008). Corrosion Monitoring, n.p.

 Karen, (2013). The high cost of corrosion- is your plant at risk?

 Lipson, LesterVern Colwell, (1961). Handbook of Mechanical Wear: wear Frettage. ASM

Handbook, Vol. 13 “Corrosion”, ASM International, (1987)

 Linda Garverick, (1994). “Technology and Engineering”. Petroleum in the petrochemical

industry.

 Matthew Avery, Benjamin Chui, Y. Gordon Kariya, Kenneth Larson, (2001). Hydrogen

Induced Corrosion. Material Science 112 Group Research Paper.

 Mohd. HanifDewan, IENG, IMarEng, MIMarEST (UK), MRINA (UK), n.d. “Corrosion in

metals”.

 Mihn N. Nguyen, Xiaoming Wang and Robert H. Leicester, (2012). Climate change impacts

on corrosion of metal fasteners in timber construction. WCTE (World Conference On Timber

Engineering).

 Nyborg Rolf.Institute for Energy Technology, (2010). CO2 Corrosion Models for Oil and

Gas Production Systems. NACE Corrosion 2010, Conference and Expo. Paper 10371.

 P.T. Gilbert, (1956). Metallurgical reviews 1, pg. 379.

85
 P. Ofoeyeno, U. Osokogwu and A. B. O iji. Department of petroleum and Gas Engineering,

University of Port Harcourt, (2014). Analytical Modeling Of Pipeline Failure In Multiphase

Flow Due To Corrosion In Niger Delta Region. Science Africana, Vol. 13 (No. 1). Pg. 77-88.

 Raffaele Landolfo, CasciniLucrezia, Francesco Portioli (2010). Modelling of Metal structure

Corrosion Damage: A state of the Art Report. Sustainability 2010, 2, 2163-2175.ISSN 2071-

1050.

 SourabhDhawan, Harindersingh, Ranjit Singh, (2015). Erosion Behavior of Stainless Steel

Grade-316. IOSR Journal of Mechanical and Civil Engineering. (IOSR-JMCE). Pg. 58-63.

 Terence Bell, (2016). Types of Corrosion.

 Wheeler, Gerson J, (1972). The design of electronic equipment: a manual for production and

manufacturing, Prentice Hall.

 Zhi Wang, Xian-yu JIN, Nan-guo JIN, Xiang-Lin GU, Chuan-qing FU, (2014). Cover

Cracking Model in Reinforced Concrete Structures Subject to Rebar Corrosion. Journal of

Zhejiang University-Science A (Applied Physics and Engineering).

 Article from Northwest Pipe Company, n.d. Corrosion Control-Linings-Coatings.

 Article published the National Physical Laboratory, n.d. Stress Corrosion Cracking.

86